Anthraquinone derivative and process of preparing the same



Patented Mar. 6, 1934 UNITED STATES ANTHRAQUINONE DERIVATIVE AND PROC-ESS F PREPARING THE SAME Alexander J. Wuertz, Carrollville, Wis.,assignor to E. I. du Pont de Nemours & Company, Wilmington, Del, acorporation of Delaware No Drawing. Original application May 21, 1929,Serial No. 364,943. Divided and this application September 14, 1932,Serial No. 633,081

8 Claims.

This application is a division of my copending application Serial No.364,943, filed May 21, 1929. The invention herein set forth relates tonew anthraquinone derivatives which are useful as intermediates for vatdyestuffs. More particularly, it relates to dicarboxylic acidderivatives of anthraquinone which are typified by the formula (I EN 2(wherein one of the substituents X, Y and Z represents the radical o 0on The prior art patents German #237,236; British' #894 of 1911; French#425,859 and United States #1,011,068 deal with the condensationproducts of halogen-anthraquinone derivatives with primary aminoderivatives where one but not both derivatives contains a carboxylicacid group. The resultant products thus obtained where the carboxylicacid groups are in the ortho-position to the (NI-I) radical regardlessof whether the groups are in the anthraquinone nucleus or inthesubstituent radical (R).

Furthermore, it is of general knowledge in the field of anthraquinonechemistry that, when there is present as in the above compounds acarboxylic acid group in a dianthraquinonylamine derivative or in ana'nthraquinone-phenyl- 60 amino derivative as well as in ananthraquinonenaphthyl-amino derivative, if said carboxylic acid group isin the ortho position or adjacent to the amino group, the formation ofthe acridone structure takes place upon subjecting these compounds to atreatment with such condensing agents as phosphorous pentachloride,thionyl chloride, acetyl chloride, phosgene, benzo-trichloride or evenconcentrated sulphuric acid. These general principles may be illustratedby the following example:

11 O n i 0 =0 Other examples could be given. However, these will sufiicefor illustrating the fundamental principles under consideration.

The acridone dyes prepared from such intermediates, however, with thepossible exception of two or three, have poor covering power on thefiber and furthermore they have a tendency to bleed, which, obviously,is disadvantage.

This being the present state of the art, the primary object of thepresent invention is therefore the preparation of vat dyes of theanthraquinone-acridone type which are free from the objections common tothe dyes of this type heretofore known. Another object is thepreparation of intermediates from which the new dyes may be prepared.

With these objects in view I have conceived the idea that if a newanthraquinone derivative could be prepared which had a carbonyl chloridegrouping, it would be possible to prepare a new line of valuable colorswhich would have the advantages of both an acridone as well as acarbonyl-imid structure. The anthraquinoneacridone molecule was deemedsuitable for this purpose.

These objects are accomplished by the following discoveries:

When 1 halogen-anthraquinone-2-carboxylic I acid is condensed with sucharomatic primary amino-carboxylic acids as anthranilic, metaandpara-amino-benzoic acids or naphthyl-aminocarboxylic acids in a mediumof an alkaline solution and in the presence of a catalyst as a coppersalt, preferably cupric chloride or copper sulphate, a reaction ensueswhich results in the formation of dicarboxylic acid derivatives ofanthraquinone, which, to my knowledge, are novel and are not recorded inthe literature.

hese new acids have the following probable structures, each onecorresponding to the respective aromatic amino-carboxylic acid fromwhich they may be derived:

O C OH HN- 1) i G OH o Ortho-derivative EN I Meta-derivative 0 HN o f OHon A Q/ o Para-derivative As already noted, the foregoing compounds byvirtue of having one carboxylic acid group in the ortho position to the(NI-I) linkage are capable of forming anthraquinone acridones whentreated with such condensing agents as an excess of thionyl chloride ora slight excess of phosphorus pentachloride, or other suitablecondensing agents, in a medium of an inert solvent such as nitrobenzene,solvent naphtha, dichlorobenzene or toluene. At the same time thecarboxylic acid group is converted into a carbonyl-chloride group, withthe result that the final product is an anthraquinone-phenyl-acridone,having a 0001 group in the phenyl nucleus.

The chemical behavior of these anthraquinonephenyl-acridone-carbonylchlorides is of unusual importance to the synthesis of new vat dyes.They will readily condense with aliphatic and aromatic primary amines toform pink and violet colors. Furth rmore, they lend themselves quitereadily to simple condensations with all the amino derivatives ofanthraquinone, producing colors which fall into the fast orange shades.

The invention will now be described more particularly as to its variousphases.

As already indicated the first step in the preparation of the new dyesinvolves the preparation of the di-carboxylic acid derivatives ofanthraquinone. The following examples will illustrate the generalprocedure for the derivation of the aforesaid compounds.

Example 1 200 parts of 1-chloro-anthraquinone-2-carboxylic acid and100-110 parts of para-amino-benzoic acid are suspended in 2000-2500parts of Water. This suspension is then made alkaline with a sufficientquantity of caustic soda (solid or solution) to just turn the solutionto the alkaline side. Both of the carboxylic acids will go into solutionunder these conditions. To this solution are then added 600-800 parts ofsodium or potassium carbonate and 25-50 parts of cupric chloride and thewhole is heated to the boiling point 7 104 C.) and maintained at thispoint for a period of six to eight hours, or until no further deepeningof the color takes place. The solution is then diluted with twice itsoriginal volume of hot water and filtered directly. The filtrate willcontain the dicarboxylic acid sought in the form of its sodium salt, andthe residue will consist of copper salts and small amounts ofby-products of an indefinite constitution. In order to isolate the freeacid it is only necessary to acidify the filtrate with a mineral acidsuch as dilute hydrochloric or dilute sulphuric acid and by filteringoff the precipitate a pure product is obtained which, after drying, isan orange-red 105 powder, soluble in alkaline solution and insoluble indilute acids, but soluble in strong sulphuric acid (colorless orslightly yellow solution).

Instead of using para-amino-benzoic acid, meta-amino-benzoic acid andortho-amino-benzoic acid as well as the amino naphthoic acids may beused under the conditions similar to those described above, whereuponthe corresponding dicarboxylic acids are obtained.

Example 2 200 parts of 1-chlor-anthraquinone-2-carboxylic acid and110-120 parts of para-aminosalicylic acid are suspended in 2000-2500parts of water and made alkaline as indicated in Example 1. 600-800parts of sodium carbonate are then added, followed by 25-50 parts ofcupric chloride and the charge is heated in the same manner as in theprevious example. Under these conditions there is obtained adicarboxylic acid which contains a hydroxyl-group in the phenylaminenucleus. This product has the following configuration:

f on and consists of a violet powder, extremely soluble in an alkalinesolution and in general has similar 14) properties to the productsdescribed in Example 1. Instead of using para-amino-salicylic acid theisomeric metaand ortho-derivatives may be used, thus arriving at therespective isomeric hydroxy-dicarboxylic acids. 1 5

In the above examples the cupric chloride is employed as a catalyst forthe reaction.

It is to be understood that the examples furnished above are presentedfor purposes of illustration only, and that applicant does not intend'50 to be limited to the particular reagents and conditions thereinspecified.

Thus, the invention contemplates, in the preparation of thedi-carboxylic acid derivatives of anthraquinone, illustrated in Examples1 and 2, the use of any catalyst agent adapted to promote the reactiondesired. For example, copper powder and cuprous chloride may besubstituted for the cupric chloride employed in the examples.

Furthermore, it will be understood that the compounds employed in thepreparation of the dicarboxylic acid derivatives of anthraquinone maycontain substituent groups in the aryl nuclei, such, for example, ashalogen. It, of course, follows that the anthraquinone carbonylchlorides will contain corresponding substituents.

As many apparently widely difierent embodiments of this invention may bemade without departing from the spirit thereof, it is to be understoodthat I do not limit myself to the foregoing examples or descriptionexcept as indicated in the following claims.

I claim:

1. A compound which in the form of free acid is represented by theformula wherein R represents an aryl radical of the henzene ornaphthalene series.

2. A compound of the type set forth in claim 1 wherein R represents abenzene nucleus.

3. A compound of the type set forth in claim 1 wherein It represents abenzene nucleus and the carboxylic group is in the position para to theamino group.

4. The process of preparing a dyestufi intermediate which comprisescondensing a l-chlor-anthraquinone-Z-carboxylic acid with an aromaticprimary amino-carboxylic acid of the benzene or naphthalene series in analkaline medium and in the presence of a condensation catalyst.

5. A compound of the type set forth in claim 1 wherein R represents anaphthalene nucleus.

6. The process of preparing a dyestufi intermediate which comprisescondensing a -1-chloranthraquinone-2-carboxylic acid withparaamino-benzoic acid in an alkaline medium and in the presence of acondensation catalyst.

7. The process of preparing a dyestuff intermediate which comprisescondensing a l-chloranthraquinone-Z-carboxylic acid withparaamino-salicylic acid in an alkaline medium and in the presence of acondensation catalyst.

8. A compound which in the form of free acid possesses the formulaHNGOOOH 0 COOH ALEXANDER J. WUERTZ.

